US4714481A - Gas separation membrane - Google Patents

Gas separation membrane Download PDF

Info

Publication number
US4714481A
US4714481A US06/530,598 US53059883A US4714481A US 4714481 A US4714481 A US 4714481A US 53059883 A US53059883 A US 53059883A US 4714481 A US4714481 A US 4714481A
Authority
US
United States
Prior art keywords
sub
membrane
polymer
gas separation
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US06/530,598
Inventor
Junichi Matsuura
Munehisa Okada
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Kasei Corp
Original Assignee
Mitsubishi Kasei Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Kasei Corp filed Critical Mitsubishi Kasei Corp
Assigned to MITSUBISHI CHEMICAL INDUSTRIES LIMITED reassignment MITSUBISHI CHEMICAL INDUSTRIES LIMITED ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: MATSUURA, JUNICHI, OKADA, MUNEHISA
Application granted granted Critical
Publication of US4714481A publication Critical patent/US4714481A/en
Assigned to MITSUBISHI KASEI CORPORATION reassignment MITSUBISHI KASEI CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: MITSUBISHI CHEMICAL INDUSTRIES LIMITED
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42

Definitions

  • This invention concerns a gas separation membrane using an organic silicon polymer as the material for the membrane.
  • a high separation factor and a high permeation rate to gases are required for a gas separation membrane.
  • a structure may be considered in which a membrane layer substantially contributing to the separating function is provided at a thickness as thin as possible and supported on a porous layer.
  • a method of overlaying thin films on a porous layer which are prepared separately to each other a method of forming an anisotropic membrane at once in which a surface layer and a porous layer are present together and a method of forming a thin film by carrying out in situ polymerization, on a porous layer, from a monomer by way of various processes or a method of forming a thin film by coating a solution of polymer and then evaporating a solvent.
  • Silicon-containing polymers are generally known as the material having the highest gas permeability coefficient (value represented by the volume of a gas in cm 3 which permeates through a film of 1 cm thickness, at the film area 1 cm 2 for one second with the pressure difference of 1 cmHg), and polysiloxane, block copolymers of polysiloxane with polycarbonate, styrene, phenolic resin or the like, and polyvinyltrimethylsilane have, for example, been employed as the material for the gas separation membrane.
  • gas permeability coefficient value represented by the volume of a gas in cm 3 which permeates through a film of 1 cm thickness, at the film area 1 cm 2 for one second with the pressure difference of 1 cmHg
  • polysiloxane is the material having the highest permeability coefficient
  • its possible thickness when formed into a thin film is restricted due to the low strength thereof.
  • Materials improved with the defect in a strength include, for example, polysiloxane-polycarbonate copolymer, polysiloxane-styrene copolymer and polysiloxane-phenolic resin copolymer and they are formed into a thin film and overlayed with a porous film prepared separately for use.
  • polyvinyltrimethylsilane can be formed into an anisotropic membrane of a thin film thickness and a dense structure and used, as the gas separation membrane.
  • the membrane material of a polymer having the main repeating unit of the formula ##STR3## and/or formula ##STR4## is a polymer having carbon-carbon bonds in the main chain and silicon atoms on the side chain of the polymer in the same manner as in polyvinyltrimethylsilane having the repeating unit of the formula ##STR5## and the similar separating function has been anticipated. As the result of the study, we have however found that a characteristically excellent separating function can be obtained as compared with polyvinyltrimethylsilane and have accomplished the present invention.
  • the gist of the present invention concerns a gas separation membrane using, as the membrane material, a polymer having the main repeating unit of the formula ##STR6## and/or the formula ##STR7## (wherein R represents alkyl group, vinyl group, allyl group, cycloalkyl group, aryl group, benzyl group or hydrogen atom, each R being possibly identical or different to each other) and having a number average molecular weight of between 1,000-1,000,000 and preferably 2,000-100,000, or a partially or wholly hydrogenated product of the polymer with respect to the unsaturated bonds therein.
  • the polymer mainly comprising the repeating unit of the formula ##STR8## and/or the formula ##STR9## can be obtained by polymerizing a triorganoethynylsilane of the formula ##STR10## and/or a bistriorganosilylacetylene of the formula ##STR11## as the main starting material.
  • the polymer and hydrogenated product thereof excepting polytriorganosilane are novel silicone polymers and we have found that they are best suited as the material for the gas separation membrane having excellent gas permeating function and excellent separating function between gases and have attained the present invention.
  • FIGS. 1 and 2 are infrared absorption spectrum charts for one example of the polymer used as the membrane material in the present invention.
  • the polymer used as the material for the gas separation membrane according to the present invention can be produced by polymerizing or copolymerizing a triorganoethynylsilane having the formula ##STR12## and/or a bistriorganosilylacetylene of the formula ##STR13## (wherein R has the same meanings as R in the previous formula).
  • Examples of monomers represented by the formula ##STR14## include, for example, trimethylethynylsilane, triethylethynylsilane, tri-n-propylethynylsilane, tri-i-propylethynylsilane, tri-n-butylethynylsilane, tri-i-butylethynylsilane, dimethylethylethynylsilane, methyldiethylethynylsilane, dimethyl-n-propylethynylsilane, methylethyl-n-propylethynylsilane, tri-n-hexylethynylsilane, dimethylvinylethynylsilane, dimethylallylethynylsilane, diethylvinylethynylsilane, diethylallylethynylsilane, methyldial
  • examples of monomers represented by the formula ##STR15## include, for example, bis(trimethylsilyl)acetylene, bis(triethylsilyl)acetylene, bis(tri-n-propylsilyl)acetylene, bis(tri-n-butylsilyl)acetylene, bis(tri-i-propylsilyl)acetylene, bis(tri-i-butylsilyl)acetylene, bis(triphenylsilyl)acetylene, bis(tricyclohexylsilyl)acetylene, bis(tribenzylsilyl)acetylene, bis(dimethylphenylsilyl)acetylene and bis(diphenylmethylsilyl) acetylene.
  • R in the above mentioned formula is an alkyl group or a phenyl group are particularly preferred.
  • Polymerization for these monomers, triorganoethynylsilane and bistriorganosilylacetylene are carried out according to the polymerizing process for various acetylene derivatives as described in Japanese Patent Publication Nos. 37312/1976, 20511/1977, 30722/1980, 43037/1979 and 23565/1980.
  • tungsten hexachloride or molybdenum pentachloride is used as a main catalyst and a tin compound such as tetraphenyltin, alcohols, ketones and ethers are used together as a second ingredient.
  • the ratio of the main catalyst and the second ingredient is preferably between 0.01-10 in the molar ratio of the second ingredient/main catalyst.
  • the ratio of the monomer to the main catalyst is in a range of less than 1,000.
  • the solvent usable in the reaction includes aromatic hydrocarbon such as benzene and toluene and halogenated hydrocarbon such as ethylenedichloride and carbon tetrachloride.
  • the reaction temperature for the polymerization is preferably between -10°-50° C.
  • the reaction time although different depending on the reaction conditions, is usually selected between 0.1-100 hours. After the completion of the polymerizing reaction, the reaction product can be collected, for example, by pouring it into methanol and depositing the resultant polymer.
  • the polymerizing process has been examplified as above, it is not restricted to these processes. Copolymerization with other acetylene derivatives not containing silicon is also possible.
  • hydrogenated product of the polymer obtained through the polymerization or copolymerization can also be used as the material for the gas separation membrane according to this invention.
  • a portion or substantially the whole portion that is, a ratio of from 0 to 100%, preferably, from 0 to 80% of the unsaturated bonds present in the polymer can be reacted and all of these hydrogenated products can be used as the material for the gas separation membrane according to this invention.
  • nickel catalyst for instance, Raney nickel
  • cobalt platinum, palladium, ruthenium, rhodium catalyst, a mixture thereof or an alloy catalyst
  • These catalyst can be used solely, as solid or uniform soluble complex, or in the form supported on carbon, silica, alumina or diatomaceous earth.
  • hydrogenation may also be conducted by using a metal complex obtained by reducing a compound containing nickel, titanium, cobalt or the like with an organic metal compound (for example, trialkylaluminum and alkyllithium).
  • Hydrogen usable herein is usually molecular hydrogen but hydrogen-containing gases can also be used so long as they do not contain substances acting as a catalyst poison.
  • the hydrogen pressure may be that of an ambient pressure flow or of a pressurized system.
  • the temperature is from room temperature to 200° C. and, preferably, of less than 180° C.
  • the organic silicon polymer obtained in this way is then formed into a film, in which film forming method has no particular restriction.
  • Preferred film forming methods include a method of applying a coating on a porous film prepared separately, and a method of forming an anisotropic film comprising a dense surface layer and a porous layer.
  • the organic silicon polymer is dissolved in an organic solvent, a porous membrane composed of a different material formed separately into a film is immersed in the solution and, thereafter, the organic solvent is dried.
  • the organic solvent used for dissolving the polymer into a film-forming solution has no particular restriction so long as it is a solvent capable of dissolving the polymer, having a low boiling point thus being removed with relatively ease and not dissolving the porous membrane as the support.
  • benzene, toluene, pentane, hexane, heptane and tetrahydrofuran can be mentioned while depending on the kind of material for the porous membrane.
  • the porous membrane for use in the present invention involves such a membrane as having a sponge-like structure and including pores opened to both surfaces thereof, or such a membrane having a dense layer on one surface of the membrane and opened pores at the other surface, or a membrane having ultrafine micro-pores in the molecular point of view, with the permeation rate for the nitrogen gas of more than 1 ⁇ 10 -4 cm 3 /cm 2 .sec.cmHg in the permeation volume per unit membrane area (1 cm 2 ) for unit time (1 sec) with unit pressure difference (1 cmHg).
  • Such a membrane can be prepared by various methods for example, by adding an organic solvent or an additive to the material for the porous membrane to form a film and, thereafter, leaching out the organic solvent or the additive.
  • the kind of the materials for the porous membrane has no particular restriction and it includes, for example, polypropylene, polyvinyl chloride, polystyrene, polyvinyl alcohol, polymethyl methacrylate, polyacrylonitrile, polycarbonate, polyphenyleneoxide, polyamide, polysulfone, polyethersulfone, polysulfoneamide, polypiperazine, cellulose acetate, cellulose acetate butyrate, polytetrafluoroethylene (Teflon), vinylidene fluoride, polyvinyltrimethylsilane and those polymers containing polyaminoacid structure.
  • polypropylene polypropylene
  • polyvinyl chloride polystyrene
  • polyvinyl alcohol polymethyl methacrylate
  • polyacrylonitrile polycarbonate
  • polyphenyleneoxide polyamide
  • polysulfone polyethersulfone
  • polysulfoneamide polypiperazine
  • cellulose acetate cellulose acetate but
  • inorganic materials such as glass can also be used.
  • the concentration of the solution in the case of dissolving the organic silicon polymer into the organic solvent for covering on the porous membrane is between 0.1-50% by weight and, preferably, between 1-10% by weight, while different depending on the molecular weight of the polymer, molecular weight distribution and the kind of the solvent.
  • the concentration is lower than 0.1% by weight, the thickness of the coating film becomes thinner as well, whereby no sufficient separating function can be obtained although the gas permeation rate is higher.
  • the concentration is higher than 50% by weight, the thickness of the coating membrane is increased to decrease the gas permeation rate although the separating performance can be achieved.
  • the coating amount of the polymer is usually selected within such a range as providing 0.01-10 mg per 1 cm 2 area of the porous membrane.
  • the thickness of the porous membrane is preferably, between 10 ⁇ -100 ⁇ although it is not particularly restricted.
  • the method of coating the organic silicon polymer on the porous membrane has no particular restriction and it can be carried out by the method of immersing the porous membrane into the polymer solution or by a method of casting the polymer solution on the surface of the porous membrane.
  • the membrane can be used in any of the configurations such as fiberous form, tubular form, spiral form and plateous form (the configuration of the porous membrane may be selected in the case of applying the coating on the porous membrane),
  • the coating layer is further laminated by way of plasma polymerization, etc on the surface of the membrane according to the present invention.
  • the permeation velocity can be improved by mixing or bonding a polymer having polysiloxane couplings to the organic silicon polymer as the material for the membrane.
  • GPC gel permeation chromatography
  • the GPC measurement was carried out under the conditions: at 5000H, 4000H, 3000H, 2000H of an RI-8 type detector column TSK-G, manufactured by Toyo Soda, using tetrahydrofuran as the solvent, flowing rate of 1 ml/min, at 45° C., and with a monodispersed polystyrene manufactured from Pressure Chemical (USA), and all of the values were converted as polystyrene.
  • the number average molecular weight and the weight average molecular weight converted as polystyrene were 5,000 and 21,600 respectively, with Mw/Mn being 4.33.
  • the product is a polymer having repeating unit of the formula ##STR18##
  • Example 2 The same reaction and after-treatments as in Example 1 were carried out excepting the use of molybdenum pentachloride and tetraphenyltin as the catalyst to obtain 1.2 g of product.
  • the number average molecular weight (Mn) and the weight average molecular weight (Mw) converted as styrene were 3,700 and 6,200 respectively, with Mw/Mn being 1.7.
  • Example 2 The same reaction and after-treatments as in Example 1 were carried out excepting the use of 2 mmol of tungsten hexachloride and tetraphenyltin as the catalyst, 50 ml of toluene as the solvent, 5.0 g of trimethylethynylsilane and 5.0 g of bis(trimethylsilyl)acetylene as the monomer to obtain 1.81 g of solid polymer.
  • Example 5 The same reaction and after-treatments as in Example 5 were carried out excepting the use of 7.5 g of trimethylethynylsilane and 2.5 g of bis(trimethylsilyl) acetylene as the monomer to obtain 3.84 g of solid polymer.
  • Example 2 To a 200 ml of autoclave, were charged 1.6 g of polytrimethylethynylsilane obtained in Example 1, 0.8 g of ruthenium catalyst supported on carbon, 66.2 g of normal heptane and 3.8 g of isopropanol, and they were reacted at 150° C. and under a hydrogen pressure of 35 kg/cm 2 G for one hour. After the reaction was over, the catalyst was eliminated by filtration and the solvent was removed from the filtrate through evaporation to obtain a hydrogenation product. In the infrared absorption spectrum for the product, decrease in the absorption for the double-bond was observed near 1,570 cm -1 (refer to FIG. 1.
  • Example 8 The same reaction as in Example 8 was carried out excepting the use of toluene instead of normal hexane as the solvent to obtain a product with 40% hydrogenating rate calculated due to the decrease in the absorption of double bond near 1,570 cm -1 in the infrared spectrum.
  • Example 1 Polytrimethylethynylsilane obatained in Example 1 was dissolved into toluene to prepare a 5% by weight solution.
  • VSWP average pore size of 0.025 ⁇
  • the membrane was installed in a permeation test device for measuring the permeation rate for various type of gases.
  • the surface area of the membrane was 12.56 cm 2 , each of high purity gases was taken out from a gas bomb and brought to contact with the high pressure side of the membrane under a control pressure of 2 atm., the permeated gas was collected on the opposite side of the membrane under the atmospheric pressure and a permeation amount was measured in a gas burette with elapse of time.
  • the temperature of the gas and the device was 23°-25° C.
  • the permeation velocity for each type of the gases was represented by converting the volume (cc) of each gas permeating per unit area (1 cm 2 ), per unit pressure difference (1 cmHg) and per unit time (1 sec) into the normal state.
  • the separating factor was represented by the ratio of the permeation rate between each type of gases.
  • Membrane was prepared in the same manner as in Example 10 excepting by dissolving the copolymer of trimethylethynylsilane and bis(trimethylsilyl)acetylene obtained in Example 5 into about 2% toluene solution and the permeation rate was measured for each kind of gases. Further, separating factor was represented by the ratio thereof.
  • Hydrogenated product of polytrimethylethynylsilane obtained in Example 7 was dissolved in toluene to prepare a 5% by weight of solution.
  • VSWP average pore size of 0.025 ⁇
  • the membrane was installed in a permeation test device and permeation rate for each kind of gases was measured in the same manner as in Example 10.
  • the separating factor of polyvinyltrimethylsilane described in the Examples 3 and 4 of Japanese Patent Laid-Open No. 2093/1971 when calculated based on the permeation rate thereof is as below:
  • Example 6 The same film formation and the measurement for the permeation velocity as in Example 6 were carried out excepting that immersion was conducted for one min in a 5% toluene solution of polytrimethylethynylsilane obtained in Example 4.
  • Example 13 The same film formatiom was carryed out as in Example 13 excepting that 0.25 g of the hydrogenated product of polytrimethylethynylsilane obtained in Example 8 were dissolved in 5 g of toluene, and the permeation rate for various kind of gases was measured.
  • the separating factor was represented by the ratio thereof.
  • Example 4 The same reaction as in Example 4 was carried out excepting the use of 131 g of trimethylethynylsilane as the monomer and 17.4 g of 2-octyne as other acetylene compound to obtain 70 g of product.
  • Membrane formation was carried out in the same manner as in Example 10 excepting that 0.16 g of the hydrogenation product of the copolymer of polytrimethylethynylsilane and 2-octyne obtained in Example 16 were dissolved in 5 g of toluene and the permeation rate for each kind of gases was measured.
  • the separating factor was represented as the ratio thereof.
  • the membrane according to the present invention can be employed for separating a gas mixture, particularly, containing at least one of the gases of oxygen, nitrogen, gaseous carbon dioxide, carbon monoxide, hydrogen, helium, methane and argon from each other.
  • it can be applied to the separation between nitrogen and oxygen in the production of oxygen-enriched air, separation between methane and helium in the recovery of helium from natural gases, separation between argon and hydrogen, methane and hydrogen and nitrogen and hydrogen in the recovery of hydrogen from hydrogenating reaction exhaust gases, separation between carbon monooxide and hydrogen in the recovery of hydrogen from cracking gases, separation between carbon dioxide and nitrogen in the recover of carbon dioxide from combustion gases.

Abstract

A gas separation membrane using, as the material for the membrane, a polymer having the main repeating unit of the formula: ##STR1## and/or formula: ##STR2## (where R represents alkyl group, vinyl group, allyl group, cycloalkyl group, aryl group, benzyl group or hydrogen atom, each R being possibly identical or different to each other) and having the number average molecular weight of between 1,000-1,000,000, or a partially or wholly hydrogenated product of said polymer with the unsaturation bonds therein.

Description

TECHNICAL FIELD
This invention concerns a gas separation membrane using an organic silicon polymer as the material for the membrane.
BACKGROUND ART
A high separation factor and a high permeation rate to gases are required for a gas separation membrane.
For satisfying such a performance, a structure may be considered in which a membrane layer substantially contributing to the separating function is provided at a thickness as thin as possible and supported on a porous layer.
Various methods have been devised for the process of producing membranes of such a structure.
There can be mentioned, for instance, a method of overlaying thin films on a porous layer which are prepared separately to each other, a method of forming an anisotropic membrane at once in which a surface layer and a porous layer are present together and a method of forming a thin film by carrying out in situ polymerization, on a porous layer, from a monomer by way of various processes or a method of forming a thin film by coating a solution of polymer and then evaporating a solvent.
Silicon-containing polymers are generally known as the material having the highest gas permeability coefficient (value represented by the volume of a gas in cm3 which permeates through a film of 1 cm thickness, at the film area 1 cm2 for one second with the pressure difference of 1 cmHg), and polysiloxane, block copolymers of polysiloxane with polycarbonate, styrene, phenolic resin or the like, and polyvinyltrimethylsilane have, for example, been employed as the material for the gas separation membrane.
Among these silicon-polymers, although polysiloxane is the material having the highest permeability coefficient, its possible thickness when formed into a thin film is restricted due to the low strength thereof. Materials improved with the defect in a strength include, for example, polysiloxane-polycarbonate copolymer, polysiloxane-styrene copolymer and polysiloxane-phenolic resin copolymer and they are formed into a thin film and overlayed with a porous film prepared separately for use. Further, polyvinyltrimethylsilane can be formed into an anisotropic membrane of a thin film thickness and a dense structure and used, as the gas separation membrane.
The membrane material of a polymer having the main repeating unit of the formula ##STR3## and/or formula ##STR4## is a polymer having carbon-carbon bonds in the main chain and silicon atoms on the side chain of the polymer in the same manner as in polyvinyltrimethylsilane having the repeating unit of the formula ##STR5## and the similar separating function has been anticipated. As the result of the study, we have however found that a characteristically excellent separating function can be obtained as compared with polyvinyltrimethylsilane and have accomplished the present invention.
DISCLOSURE OF INVENTION
The gist of the present invention concerns a gas separation membrane using, as the membrane material, a polymer having the main repeating unit of the formula ##STR6## and/or the formula ##STR7## (wherein R represents alkyl group, vinyl group, allyl group, cycloalkyl group, aryl group, benzyl group or hydrogen atom, each R being possibly identical or different to each other) and having a number average molecular weight of between 1,000-1,000,000 and preferably 2,000-100,000, or a partially or wholly hydrogenated product of the polymer with respect to the unsaturated bonds therein.
The polymer mainly comprising the repeating unit of the formula ##STR8## and/or the formula ##STR9## can be obtained by polymerizing a triorganoethynylsilane of the formula ##STR10## and/or a bistriorganosilylacetylene of the formula ##STR11## as the main starting material. The polymer and hydrogenated product thereof excepting polytriorganosilane are novel silicone polymers and we have found that they are best suited as the material for the gas separation membrane having excellent gas permeating function and excellent separating function between gases and have attained the present invention.
BRIEF DESCRIPTION OF DRAWINGS
FIGS. 1 and 2 are infrared absorption spectrum charts for one example of the polymer used as the membrane material in the present invention.
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention will now be explained more in detail.
The polymer used as the material for the gas separation membrane according to the present invention can be produced by polymerizing or copolymerizing a triorganoethynylsilane having the formula ##STR12## and/or a bistriorganosilylacetylene of the formula ##STR13## (wherein R has the same meanings as R in the previous formula).
Examples of monomers represented by the formula ##STR14## include, for example, trimethylethynylsilane, triethylethynylsilane, tri-n-propylethynylsilane, tri-i-propylethynylsilane, tri-n-butylethynylsilane, tri-i-butylethynylsilane, dimethylethylethynylsilane, methyldiethylethynylsilane, dimethyl-n-propylethynylsilane, methylethyl-n-propylethynylsilane, tri-n-hexylethynylsilane, dimethylvinylethynylsilane, dimethylallylethynylsilane, diethylvinylethynylsilane, diethylallylethynylsilane, methyldiallylethynylsilane, triallylethynylsilane, di-n-propylallylethynylsilane, triphenylethynylsilane, diphenylmethylethynylsilane, diphenylethylethynylsilane, diphenyl-n-propylethynylsilane, dimethylphenylethynylsilane, diethylphenylethynylsilane, di-n-propylphenylethynylsilane, tricyclohexylethynylsilane, dimethylcyclohexylethynylsilane, diphenylcyclohexylethynylsilane, dimethylhydroethynylsilane and tribenzylethynylsilane.
Further, examples of monomers represented by the formula ##STR15## include, for example, bis(trimethylsilyl)acetylene, bis(triethylsilyl)acetylene, bis(tri-n-propylsilyl)acetylene, bis(tri-n-butylsilyl)acetylene, bis(tri-i-propylsilyl)acetylene, bis(tri-i-butylsilyl)acetylene, bis(triphenylsilyl)acetylene, bis(tricyclohexylsilyl)acetylene, bis(tribenzylsilyl)acetylene, bis(dimethylphenylsilyl)acetylene and bis(diphenylmethylsilyl) acetylene.
Among these monomers, those in which R in the above mentioned formula is an alkyl group or a phenyl group are particularly preferred. Polymerization for these monomers, triorganoethynylsilane and bistriorganosilylacetylene are carried out according to the polymerizing process for various acetylene derivatives as described in Japanese Patent Publication Nos. 37312/1976, 20511/1977, 30722/1980, 43037/1979 and 23565/1980. Specifically, tungsten hexachloride or molybdenum pentachloride is used as a main catalyst and a tin compound such as tetraphenyltin, alcohols, ketones and ethers are used together as a second ingredient. The ratio of the main catalyst and the second ingredient is preferably between 0.01-10 in the molar ratio of the second ingredient/main catalyst. The ratio of the monomer to the main catalyst is in a range of less than 1,000. The solvent usable in the reaction includes aromatic hydrocarbon such as benzene and toluene and halogenated hydrocarbon such as ethylenedichloride and carbon tetrachloride. Further, the reaction temperature for the polymerization is preferably between -10°-50° C. The reaction time, although different depending on the reaction conditions, is usually selected between 0.1-100 hours. After the completion of the polymerizing reaction, the reaction product can be collected, for example, by pouring it into methanol and depositing the resultant polymer. Although the polymerizing process has been examplified as above, it is not restricted to these processes. Copolymerization with other acetylene derivatives not containing silicon is also possible.
In addition to the polymer obtained through polymerization of copolymerization of the triorganoethynylsilane represented by the formula ##STR16## and/or the bistriorganosilylacetylene represented by the formula ##STR17## as the main starting material, hydrogenated product of the polymer obtained through the polymerization or copolymerization can also be used as the material for the gas separation membrane according to this invention. In the hydrogenation, a portion or substantially the whole portion, that is, a ratio of from 0 to 100%, preferably, from 0 to 80% of the unsaturated bonds present in the polymer can be reacted and all of these hydrogenated products can be used as the material for the gas separation membrane according to this invention.
For the hydrogenation, means conventionally employed for the catalytic hydrogenating treatment can be used. Specifically, nickel catalyst (for instance, Raney nickel), cobalt, platinum, palladium, ruthenium, rhodium catalyst, a mixture thereof or an alloy catalyst can be used as the hydrogenating catalyst. These catalyst can be used solely, as solid or uniform soluble complex, or in the form supported on carbon, silica, alumina or diatomaceous earth. Furthermore, hydrogenation may also be conducted by using a metal complex obtained by reducing a compound containing nickel, titanium, cobalt or the like with an organic metal compound (for example, trialkylaluminum and alkyllithium). Hydrogen usable herein is usually molecular hydrogen but hydrogen-containing gases can also be used so long as they do not contain substances acting as a catalyst poison. The hydrogen pressure may be that of an ambient pressure flow or of a pressurized system. The temperature is from room temperature to 200° C. and, preferably, of less than 180° C.
The organic silicon polymer obtained in this way is then formed into a film, in which film forming method has no particular restriction.
Preferred film forming methods include a method of applying a coating on a porous film prepared separately, and a method of forming an anisotropic film comprising a dense surface layer and a porous layer.
In the method of applying a coating on a porous membrane, the organic silicon polymer is dissolved in an organic solvent, a porous membrane composed of a different material formed separately into a film is immersed in the solution and, thereafter, the organic solvent is dried.
The organic solvent used for dissolving the polymer into a film-forming solution has no particular restriction so long as it is a solvent capable of dissolving the polymer, having a low boiling point thus being removed with relatively ease and not dissolving the porous membrane as the support.
For instance, benzene, toluene, pentane, hexane, heptane and tetrahydrofuran can be mentioned while depending on the kind of material for the porous membrane.
The porous membrane for use in the present invention involves such a membrane as having a sponge-like structure and including pores opened to both surfaces thereof, or such a membrane having a dense layer on one surface of the membrane and opened pores at the other surface, or a membrane having ultrafine micro-pores in the molecular point of view, with the permeation rate for the nitrogen gas of more than 1×10-4 cm3 /cm2.sec.cmHg in the permeation volume per unit membrane area (1 cm2) for unit time (1 sec) with unit pressure difference (1 cmHg).
Such a membrane can be prepared by various methods for example, by adding an organic solvent or an additive to the material for the porous membrane to form a film and, thereafter, leaching out the organic solvent or the additive.
The kind of the materials for the porous membrane has no particular restriction and it includes, for example, polypropylene, polyvinyl chloride, polystyrene, polyvinyl alcohol, polymethyl methacrylate, polyacrylonitrile, polycarbonate, polyphenyleneoxide, polyamide, polysulfone, polyethersulfone, polysulfoneamide, polypiperazine, cellulose acetate, cellulose acetate butyrate, polytetrafluoroethylene (Teflon), vinylidene fluoride, polyvinyltrimethylsilane and those polymers containing polyaminoacid structure.
Further, inorganic materials such as glass can also be used.
The concentration of the solution in the case of dissolving the organic silicon polymer into the organic solvent for covering on the porous membrane is between 0.1-50% by weight and, preferably, between 1-10% by weight, while different depending on the molecular weight of the polymer, molecular weight distribution and the kind of the solvent.
If the concentration is lower than 0.1% by weight, the thickness of the coating film becomes thinner as well, whereby no sufficient separating function can be obtained although the gas permeation rate is higher. On the other hand, if the concentration is higher than 50% by weight, the thickness of the coating membrane is increased to decrease the gas permeation rate although the separating performance can be achieved.
The coating amount of the polymer is usually selected within such a range as providing 0.01-10 mg per 1 cm2 area of the porous membrane.
The thickness of the porous membrane is preferably, between 10μ-100μ although it is not particularly restricted.
The method of coating the organic silicon polymer on the porous membrane has no particular restriction and it can be carried out by the method of immersing the porous membrane into the polymer solution or by a method of casting the polymer solution on the surface of the porous membrane.
In either case of applying the coating on the porous membrane or forming the film by other method;
(1) the membrane can be used in any of the configurations such as fiberous form, tubular form, spiral form and plateous form (the configuration of the porous membrane may be selected in the case of applying the coating on the porous membrane),
(2) heat treatment may further be applied to the membrane after the film formation,
(3) the coating layer is further laminated by way of plasma polymerization, etc on the surface of the membrane according to the present invention, and
(4) the permeation velocity can be improved by mixing or bonding a polymer having polysiloxane couplings to the organic silicon polymer as the material for the membrane.
The content of the present invention will now be explained by way of examples but the contents of the present invention are not restricted only to such examples.
EXAMPLE 1 Synthesis for polytrimethylethynylsilane
To a 200 ml flask, were charged 100 ml of dewatered toluene, 9.8 g (0.1 mol) of trimethylethynylsilane as the monomer, and each 3 mmol of tungsten hexachloride and tetraphenyltin as the catalyst, and they were reacted at 15°-35° C. for 100 hours. After the reaction was over, methanol was added by about 10 times of volume to the reaction solution to precipitate the resultant polymer, followed by repeating filtration and methanol washing to obtain 4.5 g of product after drying.
Measurement was carried out by gel permeation chromatography (hereinafter referred to simply as GPC) for the portion of the product soluble to tetrahydrofuran.
The GPC measurement was carried out under the conditions: at 5000H, 4000H, 3000H, 2000H of an RI-8 type detector column TSK-G, manufactured by Toyo Soda, using tetrahydrofuran as the solvent, flowing rate of 1 ml/min, at 45° C., and with a monodispersed polystyrene manufactured from Pressure Chemical (USA), and all of the values were converted as polystyrene.
As the result of the GPC measurement for the product, the number average molecular weight and the weight average molecular weight converted as polystyrene were 5,000 and 21,600 respectively, with Mw/Mn being 4.33.
The result of the infrared spectrum measurement for the product is shown in FIG. 2. Absorption of the carbon-carbon conjugated double bond was observed at 1,570 cm-1.
The product is a polymer having repeating unit of the formula ##STR18##
EXAMPLE 2 Synthesis for polytrimethylethynylsilane
The same reaction and after-treatments as in Example 1 were carried out excepting the use of molybdenum pentachloride and tetraphenyltin as the catalyst to obtain 1.2 g of product.
EXAMPLE 3 Synthesis for polybis(trimethylsilyl)acetylene
To a 200 ml flask, were charged 100 ml of dewatered toluene, 8.5 g (0.05 mol) of bis(trimethylsilyl)acetylene as the monomer and each 1.5 mmol of molybdenum pentachloride and tetraphenyltin as the catalyst, and they were reacted at 15°-35° C. for 100 hours to obtain 0.3 g of product. Based on the infrared absorption spectroscopy, the product was assumed to have the repeating unit of the formula ##STR19##
EXAMPLE 4 Synthesis for polytrimethylethynylsilane
To a 2 liter flask, were charged 1.5 liter of toluene, 147 g (1.5 mol) of trimethylethynylsilane as the monomer and each 30 mmol of tungsten hexachloride and tetraphenyltin as the catalyst, and they were reacted at 23°-25° C. for 24 hours. After the reaction was over, the reaction solution was poured into methanol of about twice volume to precipitate the resultant polymer, followed by repeating filtration and methanol washing to obtain 67 g of product after drying.
As the result of the same GPC measurement as in Example 1 for the portion of the product soluble to tetrahydrofuran, the number average molecular weight (Mn) and the weight average molecular weight (Mw) converted as styrene were 3,700 and 6,200 respectively, with Mw/Mn being 1.7.
EXAMPLE 5 Synthesis for the copolymer of trimethylethynylsilane and bis(trimethylsilyl)acetylene
The same reaction and after-treatments as in Example 1 were carried out excepting the use of 2 mmol of tungsten hexachloride and tetraphenyltin as the catalyst, 50 ml of toluene as the solvent, 5.0 g of trimethylethynylsilane and 5.0 g of bis(trimethylsilyl)acetylene as the monomer to obtain 1.81 g of solid polymer.
EXAMPLE 6 Synthesis for the copolymer of trimethylethynylsilane and bis(trimethylsilyl)acetylene
The same reaction and after-treatments as in Example 5 were carried out excepting the use of 7.5 g of trimethylethynylsilane and 2.5 g of bis(trimethylsilyl) acetylene as the monomer to obtain 3.84 g of solid polymer.
EXAMPLE 7 Hydrogenating reaction for polytrimethylethynylsilane
To a 200 ml of autoclave, were charged 1.6 g of polytrimethylethynylsilane obtained in Example 1, 0.8 g of ruthenium catalyst supported on carbon, 66.2 g of normal heptane and 3.8 g of isopropanol, and they were reacted at 150° C. and under a hydrogen pressure of 35 kg/cm2 G for one hour. After the reaction was over, the catalyst was eliminated by filtration and the solvent was removed from the filtrate through evaporation to obtain a hydrogenation product. In the infrared absorption spectrum for the product, decrease in the absorption for the double-bond was observed near 1,570 cm-1 (refer to FIG. 1. Decrease in the absorption at 1,570 cm-1 was judged based on the absorbing intensity at 1,250 cm-1 or 1,410 cm-1). GPC measurement was carried out under the same conditions as in Example 1 and the thus obtained number average molecular weight and the weight average molecular weight converted as polystyrene were 6,400 and 15,300 respectively, with Mw/Mn being 2.4.
EXAMPLE 8 Hydrogenating reaction for polytrimethylethynylsilane
2.0 g of polytrimethylethynylsilane obtained in Example 4, 1.0 g of RhCl(Pφ3)3 catalyst, 45 ml of normal hexane and 5 ml of isopropanol were charged, and they were reacted at 150° C. under the hydrogen pressure of 74 kg/cm2 G for 5 hours. After the reaction was over, solid substances were removed through filtration and the filtrate was added into methanol of about 10 times volume to precipitate a polymer. The hydrogenating rate calculated due to the decrease in the absorption of the double bond near 1,570 cm-1 for the infrared absorption spectrum of the product was 42%. Mn was 4,600 and Mw was 7,300, with Mw/Mn being 1.6.
EXAMPLE 9 Hydrogenating reaction for polytrimethylethynylsilane
The same reaction as in Example 8 was carried out excepting the use of toluene instead of normal hexane as the solvent to obtain a product with 40% hydrogenating rate calculated due to the decrease in the absorption of double bond near 1,570 cm-1 in the infrared spectrum.
EXAMPLE 10 Measurement for the gas permeating performance of polytrimethylethynylsilane
Polytrimethylethynylsilane obatained in Example 1 was dissolved into toluene to prepare a 5% by weight solution.
Commercially available millipore filter, trade name, VSWP (average pore size of 0.025μ) was immersed in this solution for 2 min and then dried in air to eliminate the solvent.
The membrane was installed in a permeation test device for measuring the permeation rate for various type of gases.
The surface area of the membrane was 12.56 cm2, each of high purity gases was taken out from a gas bomb and brought to contact with the high pressure side of the membrane under a control pressure of 2 atm., the permeated gas was collected on the opposite side of the membrane under the atmospheric pressure and a permeation amount was measured in a gas burette with elapse of time. The temperature of the gas and the device was 23°-25° C.
The permeation velocity for each type of the gases was represented by converting the volume (cc) of each gas permeating per unit area (1 cm2), per unit pressure difference (1 cmHg) and per unit time (1 sec) into the normal state.
The separating factor was represented by the ratio of the permeation rate between each type of gases.
______________________________________                                    
Permeation rate                                                           
N.sub.2   2.64 × 10.sup.-7                                          
                     CC(STP)/cm.sup.2 · sec · cmHg      
O.sub.2   1.06 × 10.sup.-6                                          
                     CC(STP)/cm.sup.2 · sec · cmHg      
CO.sub.2  2.80 × 10.sup.-6                                          
                     CC(STP)/cm.sup.2 · sec · cmHg      
H.sub.2   9.24 × 10.sup.-6                                          
                     CC(STP)/cm.sup.2 · sec · cmHg      
Separating factor (ratio between the permeation rate)                     
O.sub.2 /N.sub.2                                                          
          4.0                                                             
CO.sub.2 /N.sub.2                                                         
          10.6                                                            
H.sub.2 /N.sub.2                                                          
          35.0                                                            
CO.sub.2 /O.sub.2                                                         
          2.6                                                             
H.sub.2 /O.sub.2                                                          
          8.7                                                             
H.sub.2 /CO.sub.2                                                         
          3.3                                                             
______________________________________
EXAMPLE 11 Measurement for the gas permeating performance of the copolymer of trimethylethynylsilane and bis(trimethylsilyl) acetylene
Membrane was prepared in the same manner as in Example 10 excepting by dissolving the copolymer of trimethylethynylsilane and bis(trimethylsilyl)acetylene obtained in Example 5 into about 2% toluene solution and the permeation rate was measured for each kind of gases. Further, separating factor was represented by the ratio thereof.
______________________________________                                    
Permeation rate                                                           
N.sub.2   7.6 × 10.sup.-7                                           
                    CC(STP)/cm.sup.2 · sec · cmHg       
O.sub.2   2.7 × 10.sup.-6                                           
                    CC(STP)/cm.sup.2 · sec · cmHg       
CO.sub.2  1.0 × 10.sup.-5                                           
                    CC(STP)/cm.sup.2 · sec · cmHg       
H.sub.2   1.7 × 10.sup.-5                                           
                    CC(STP)/cm.sup.2 · sec · cmHg       
separating factor (ratio between the permeation rate)                     
O.sub.2 /N.sub.2                                                          
          3.6                                                             
CO.sub.2 /N.sub.2                                                         
          13.2                                                            
H.sub.2 /N.sub.2                                                          
          22.4                                                            
CO.sub.2 /O.sub.2                                                         
          3.7                                                             
H.sub.2 /O.sub.2                                                          
          6.3                                                             
H.sub.2 /CO.sub.2                                                         
          1.7                                                             
______________________________________
EXAMPLE 12 Measurement for the gas permeating performance of hydrogenated product of polytrimethylethynylsilane
Hydrogenated product of polytrimethylethynylsilane obtained in Example 7 was dissolved in toluene to prepare a 5% by weight of solution.
A commercially available millipore filter, trade name, VSWP (average pore size of 0.025μ) was immersed in this solution for 2 min and then dried in air to eliminate the solvent.
The membrane was installed in a permeation test device and permeation rate for each kind of gases was measured in the same manner as in Example 10.
______________________________________                                    
Permeation rate                                                           
N.sub.2   6.49 × 10.sup.-7                                          
                     CC(STP)/cm.sup.2 · sec · cmHg      
O.sub.2   2.72 × 10.sup.-6                                          
                     CC(STP)/cm.sup.2 · sec · cmHg      
CO.sub.2  1.21 × 10.sup.-5                                          
                     CC(STP)/cm.sup.2 · sec · cmHg      
H.sub.2   1.93 × 10.sup.-5                                          
                     CC(STP)/cm.sup.2 · sec · cmHg      
Separating factor (ratio between the permeation rate)                     
O.sub.2 /N.sub.2                                                          
          4.2                                                             
CO.sub.2 /N.sub.2                                                         
          18.6                                                            
H.sub.2 /N.sub.2                                                          
          29.7                                                            
CO.sub.2 /O.sub.2                                                         
          4.4                                                             
H.sub.2 /O.sub.2                                                          
          7.1                                                             
H.sub.2 /CO.sub.2                                                         
          1.6                                                             
______________________________________
By the way, the separating factor of polyvinyltrimethylsilane described in the Examples 3 and 4 of Japanese Patent Laid-Open No. 2093/1971 when calculated based on the permeation rate thereof is as below:
Polytrimethylvinylsilane (Reference Example) 
______________________________________                                    
Separating factor (ratio between the permeation rate)                     
______________________________________                                    
        O.sub.2 /N.sub.2                                                  
               3.8                                                        
        CO.sub.2 /N.sub.2                                                 
               6.7                                                        
        H.sub.2 /N.sub.2                                                  
               19.1                                                       
        CO.sub.2 /O.sub.2                                                 
               2.1                                                        
        H.sub.2 /O.sub.2                                                  
               5.0                                                        
______________________________________
It is supposed that the separating factor of the gas separation membrane as described in Examples 10, 11 and 12 of the present invention has superior features as compared with that of the polyvinyltrimethylasilane membrane.
EXAMPLE 13 Measurement for the gas permeating performance of polytrimethylethynylsilane
The same film formation and the measurement for the permeation velocity as in Example 6 were carried out excepting that immersion was conducted for one min in a 5% toluene solution of polytrimethylethynylsilane obtained in Example 4.
______________________________________                                    
Permeation rate                                                           
N.sub.2   1.01 × 10.sup.-6                                          
                     CC(STP)/cm.sup.2 · sec · cmHg      
O.sub.2   4.02 × 10.sup.-6                                          
                     CC(STP)/cm.sup.2 · sec · cmHg      
CO.sub.2  1.21 × 10.sup.-5                                          
                     CC(STP)/cm.sup.2 · sec · cmHg      
H.sub.2   2.42 × 10.sup.-5                                          
                     CC(STP)/cm.sup.2 · sec · cmHg      
Separating factor (ratio between the permeation rate)                     
O.sub.2 /N.sub.2                                                          
          4.0                                                             
CO.sub.2 /N.sub.2                                                         
          12.0                                                            
H.sub.2 /N.sub.2                                                          
          24.0                                                            
CO.sub.2 /O.sub.2                                                         
          3.0                                                             
H.sub.2 /O.sub.2                                                          
          6.0                                                             
H.sub.2 /CO.sub.2                                                         
          2.0                                                             
______________________________________
EXAMPLE 14 Measurement for the gas permeating performance of polytrimethylethynylsilane
The same film formatiom was carryed out as in Example 13 excepting that 0.25 g of the hydrogenated product of polytrimethylethynylsilane obtained in Example 8 were dissolved in 5 g of toluene, and the permeation rate for various kind of gases was measured. The separating factor was represented by the ratio thereof.
______________________________________                                    
Permeation rate                                                           
N.sub.2   4.7 × 10.sup.-7                                           
                    CC(STP)/cm.sup.2 · sec · cmHg       
O.sub.2   2.1 × 10.sup.-6                                           
                    CC(STP)/cm.sup.2 · sec · cmHg       
CO.sub.2  6.9 × 10.sup.-6                                           
                    CC(STP)/cm.sup.2 · sec · cmHg       
H.sub.2   1.2 × 10.sup.-5                                           
                    CC(STP)/cm.sup.2 · sec · cmHg       
Separating factor (ratio between the permeation rate)                     
O.sub.2 /N.sub.2                                                          
          4.4                                                             
CO.sub.2 /N.sub.2                                                         
          14.7                                                            
H.sub.2 /N.sub.2                                                          
          25.5                                                            
CO.sub.2 /O.sub.2                                                         
          3.3                                                             
H.sub.2 /O.sub.2                                                          
          5.7                                                             
H.sub.2 /CO.sub.2                                                         
          1.7                                                             
______________________________________
EXAMPLE 15 Synthesis example for a copolymer of trimethylethynylsilane and other acetylene derivative
The same reaction as in Example 4 was carried out excepting the use of 131 g of trimethylethynylsilane as the monomer and 17.4 g of 2-octyne as other acetylene compound to obtain 70 g of product.
EXAMPLE 16 Hydrogenating reaction for a copolymer of polytrimethylethynylsilane and 2-octyne
50 g of the copolymer of polytrimethylethynylsilane-2-octyne obtained in Example 15, 50 g of ruthenium catalyst supported on carbon, 1.5 liter of toluene and 75 ml of isobutanol were charged in a 2 liter volume reactor, and they were reacted at 170° C., under the hydrogen pressure of 74 kg/cm2 G for 5 hours. After the reaction was over, the catalyst was removed through filtration and the solvent was eliminated from the filtrate by way of evaporation to obtain 17 g of hydrogenation product. The hydrogenating rate calculated due to the decrease in the absorption on double bond near 1,570 cm-1 in the infrared absorption spectrum for the product was 36%. Mn was 7,300 and Mw was 63,300, with Mw/Mn being 8.7.
EXAMPLE 17 Measurement for the gas permeating performance of the hydrogenation product of polytrimethylethynylsilane and 2-octyne copolymer
Membrane formation was carried out in the same manner as in Example 10 excepting that 0.16 g of the hydrogenation product of the copolymer of polytrimethylethynylsilane and 2-octyne obtained in Example 16 were dissolved in 5 g of toluene and the permeation rate for each kind of gases was measured. The separating factor was represented as the ratio thereof.
______________________________________                                    
Permeation rate                                                           
N.sub.2   2.5 × 10.sup.-6                                           
                    CC(STP)/cm.sup.2 · sec · cmHg       
O.sub.2   1.0 × 10.sup.-5                                           
                    CC(STP)/cm.sup.2 · sec · cmHg       
CO.sub.2  3.6 × 10.sup.-5                                           
                    CC(STP)/cm.sup.2 · sec · cmHg       
H.sub.2   6.6 × 10.sup.-5                                           
                    CC(STP)/cm.sup.2 · sec · cmHg       
Separating factor (ratio between the permeation rate)                     
O.sub.2 /N.sub.2                                                          
          4.0                                                             
CO.sub.2 /N.sub.2                                                         
          14.4                                                            
H.sub.2 /N.sub.2                                                          
          26.4                                                            
CO.sub.2 /O.sub.2                                                         
          3.6                                                             
H.sub.2 /O.sub.2                                                          
          6.6                                                             
H.sub.2 /CO.sub.2                                                         
          1.8                                                             
______________________________________
INDUSTRIAL APPLICABILITY
The membrane according to the present invention can be employed for separating a gas mixture, particularly, containing at least one of the gases of oxygen, nitrogen, gaseous carbon dioxide, carbon monoxide, hydrogen, helium, methane and argon from each other.
For instance, it can be applied to the separation between nitrogen and oxygen in the production of oxygen-enriched air, separation between methane and helium in the recovery of helium from natural gases, separation between argon and hydrogen, methane and hydrogen and nitrogen and hydrogen in the recovery of hydrogen from hydrogenating reaction exhaust gases, separation between carbon monooxide and hydrogen in the recovery of hydrogen from cracking gases, separation between carbon dioxide and nitrogen in the recover of carbon dioxide from combustion gases.

Claims (6)

We claim:
1. A gas separation membrane, comprising:
a membrane of a polymer having as its main repeating units, a unit of the formula: ##STR20## and/or the formula ##STR21## wherein R is an alkyl group, a vinyl group, an allyl group, a cycloalkyl group, an aryl group, a benzyl group or a hydrogen atom, with the R groups independently being identical or different, said polymer having a number average molecular weight of between 1,000-1,000,000, or a polymer having up to 80% of its unsaturated bonds hydrogenated.
2. The gas separation membrane of claim 1, wherein the material for said membrane composed of said polymer or said partially hydrogenated product of said polymer is coated onto a porous membrane.
3. The gas separation membrane of claim 2, wherein said porous membrane has a nitrogen gas permeation rate of greater than 1×10-4 cm3 /cm2 ·sec· cm Hg.
4. The gas separation membrane of claim 2, wherein said porous membrane is a material selected from the group consisting of polypropylene, polyvinylchloride, ,polystyrene, polyvinyl alcohol, polymethylmethacrylate, polyacrylonitrile, polycarbonate, polyphenyleneoxide, polyamide, polysulfone, polyethersulfone, polysulfoneamide, polypiperazine, cellulose acetate, cellulose acetate butyrate, polytetrafluoroethylene, vinylidene fluoride, and polyvinyltrimethylsilane.
5. The gas separation membrane of claim 2, wherein the amount of said silicon containing polymer coated on said porous membrane to form said gas separation membrane ranges from 0.01-10 mg per 1 cm2 of the porous membrane.
6. The gas separation membrane of claim 2, wherein the thickness of said porous membrane ranges from 10μ-100 μ.
US06/530,598 1981-11-30 1982-11-30 Gas separation membrane Expired - Fee Related US4714481A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP56192373A JPS5895541A (en) 1981-11-30 1981-11-30 Gas separating membrane
JP56-192373 1981-11-30

Publications (1)

Publication Number Publication Date
US4714481A true US4714481A (en) 1987-12-22

Family

ID=16290202

Family Applications (1)

Application Number Title Priority Date Filing Date
US06/530,598 Expired - Fee Related US4714481A (en) 1981-11-30 1982-11-30 Gas separation membrane

Country Status (3)

Country Link
US (1) US4714481A (en)
JP (1) JPS5895541A (en)
WO (1) WO1983001905A1 (en)

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4859215A (en) * 1988-05-02 1989-08-22 Air Products And Chemicals, Inc. Polymeric membrane for gas separation
US4968470A (en) * 1989-11-15 1990-11-06 Air Products And Chemicals, Inc. Asymmetric permselective polyacetylene membranes and process for the formation thereof
US5009824A (en) * 1981-12-17 1991-04-23 Hoechst Aktiengesellschaft Process for preparing an asymmetrical macroporous membrane polymer
US5011518A (en) * 1989-03-09 1991-04-30 Matsushita Electric Industrial Co., Ltd. Permselective membrane and process for producing the same
US5085676A (en) * 1990-12-04 1992-02-04 E. I. Du Pont De Nemours And Company Novel multicomponent fluid separation membranes
US5156656A (en) * 1991-09-13 1992-10-20 The Dow Chemical Company Semi-permeable membranes derived from reactive oligomers
US5176724A (en) * 1987-11-10 1993-01-05 Matsushita Electric Industrial Co., Ltd. Permselective composite membrane having improved gas permeability and selectivity
DE4213217A1 (en) * 1992-04-22 1993-10-28 Geesthacht Gkss Forschung Membrane based on graft copolymers
US5281255A (en) * 1992-11-04 1994-01-25 Membrane Technology And Research, Inc Gas-separation process
US5318706A (en) * 1991-03-06 1994-06-07 Hashimoto Chemical Co., Ltd. Method of supplying dilute hydrofluoric acid and apparatus for use in this method for supplying the acid
US5501722A (en) * 1992-11-04 1996-03-26 Membrane Technology And Research, Inc. Natural gas treatment process using PTMSP membrane
US5599380A (en) * 1994-05-20 1997-02-04 L'air Liquide, S.A. Polymeric membrane
US5707423A (en) * 1996-06-14 1998-01-13 Membrane Technology And Research, Inc. Substituted polyacetylene separation membrane
US5759237A (en) * 1996-06-14 1998-06-02 L'air Liquide Societe Anonyme Pour L'etude Et, L'exploitation Des Procedes Georges Claude Process and system for selective abatement of reactive gases and recovery of perfluorocompound gases
US5762798A (en) * 1991-04-12 1998-06-09 Minntech Corporation Hollow fiber membranes and method of manufacture
US5785741A (en) * 1995-07-17 1998-07-28 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges, Claude Process and system for separation and recovery of perfluorocompound gases
US5814127A (en) * 1996-12-23 1998-09-29 American Air Liquide Inc. Process for recovering CF4 and C2 F6 from a gas
US5855647A (en) * 1997-05-15 1999-01-05 American Air Liquide, Inc. Process for recovering SF6 from a gas
US5858065A (en) * 1995-07-17 1999-01-12 American Air Liquide Process and system for separation and recovery of perfluorocompound gases
US5919285A (en) * 1995-07-17 1999-07-06 American Air Liquide, Inc. Process and system for separation and recovery of perfluorocompound gases
USRE36914E (en) * 1992-10-07 2000-10-17 Minntech Corp Dialysate filter including an asymmetric microporous, hollow fiber membrane incorporating a polyimide
US6187077B1 (en) 1998-04-17 2001-02-13 American Air Liquide Inc. Separation of CF4 and C2F6 from a perfluorocompound mixture
US6224677B1 (en) 1995-07-17 2001-05-01 Teisan Kabushiki Kaisha Gas recovery unit utilizing dual use of gas
US20040194513A1 (en) * 2003-04-04 2004-10-07 Giacobbe Frederick W Fiber coolant system including improved gas seals

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6075306A (en) * 1983-09-30 1985-04-27 Toshinobu Higashimura Liquid separation membrane
JPS6121718A (en) * 1984-07-10 1986-01-30 Agency Of Ind Science & Technol Hydrogen permselective composite membrane and preparation thereof
JPS6135803A (en) * 1984-07-26 1986-02-20 Shin Etsu Chem Co Ltd Composite hollow yarn
US4866147A (en) * 1985-07-30 1989-09-12 The United States Of America As Represented By The United States Department Of Energy Soluble silylated polyacetylene derivatives and their use as percursors to novel polyacetylene-type polymers
US4812520A (en) * 1985-07-30 1989-03-14 The Unites States Of America As Represented By The United States Department Of Energy Method for the preparation of novel polyacetylene-type polymers

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1221404A (en) * 1968-02-12 1971-02-03 Rhone Poulenc Sa Process for the separation of gas mixtures
US3754375A (en) * 1970-03-03 1973-08-28 Rhone Poulenc Sa Anisotropic organosilicon polymer membrane
US3899309A (en) * 1972-07-20 1975-08-12 Du Pont Aromatic polyimide, polyester and polyamide separation membranes
JPS5456985A (en) * 1977-10-14 1979-05-08 Mitsubishi Chem Ind Ltd Gas-separaing membrane
US4230463A (en) * 1977-09-13 1980-10-28 Monsanto Company Multicomponent membranes for gas separations
JPS565121A (en) * 1979-06-27 1981-01-20 Sumitomo Electric Ind Ltd Heat resistant separating membrane for mixed gas
JPS5624019A (en) * 1979-08-01 1981-03-07 Matsushita Electric Ind Co Ltd Selective gas parmeable membrane
JPS5719004A (en) * 1980-07-03 1982-02-01 Nitto Electric Ind Co Ltd Composite type selective separation membrane module
JPS57122907A (en) * 1981-01-26 1982-07-31 Nitto Electric Ind Co Ltd Gas separation membrane
JPS57122906A (en) * 1981-01-22 1982-07-31 Toray Ind Inc Selective permeable film
JPS57130505A (en) * 1981-02-03 1982-08-13 Toray Ind Inc Selective permeable membrane
US4393113A (en) * 1980-06-05 1983-07-12 Teitin Limited Novel silicon-containing copolymer, ultrathin solid membrane composed of said copolymer, use of said solid membrane for concentrating a specified gas in a gaseous mixture, and process for producing said solid membrane
US4410338A (en) * 1979-06-25 1983-10-18 Kabushiki Kaisha Toyota Chuo Kenkyusho Gas separating members and a method of making the same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5221021A (en) * 1975-08-09 1977-02-17 Kubota Ltd Method of producing combined piles

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1221404A (en) * 1968-02-12 1971-02-03 Rhone Poulenc Sa Process for the separation of gas mixtures
US3754375A (en) * 1970-03-03 1973-08-28 Rhone Poulenc Sa Anisotropic organosilicon polymer membrane
US3899309A (en) * 1972-07-20 1975-08-12 Du Pont Aromatic polyimide, polyester and polyamide separation membranes
US4230463A (en) * 1977-09-13 1980-10-28 Monsanto Company Multicomponent membranes for gas separations
JPS5456985A (en) * 1977-10-14 1979-05-08 Mitsubishi Chem Ind Ltd Gas-separaing membrane
US4239793A (en) * 1977-10-14 1980-12-16 Mitsubishi Chemical Industries Ltd. Gas separation membrane
US4410338A (en) * 1979-06-25 1983-10-18 Kabushiki Kaisha Toyota Chuo Kenkyusho Gas separating members and a method of making the same
JPS565121A (en) * 1979-06-27 1981-01-20 Sumitomo Electric Ind Ltd Heat resistant separating membrane for mixed gas
JPS5624019A (en) * 1979-08-01 1981-03-07 Matsushita Electric Ind Co Ltd Selective gas parmeable membrane
US4393113A (en) * 1980-06-05 1983-07-12 Teitin Limited Novel silicon-containing copolymer, ultrathin solid membrane composed of said copolymer, use of said solid membrane for concentrating a specified gas in a gaseous mixture, and process for producing said solid membrane
JPS5719004A (en) * 1980-07-03 1982-02-01 Nitto Electric Ind Co Ltd Composite type selective separation membrane module
JPS57122906A (en) * 1981-01-22 1982-07-31 Toray Ind Inc Selective permeable film
JPS57122907A (en) * 1981-01-26 1982-07-31 Nitto Electric Ind Co Ltd Gas separation membrane
JPS57130505A (en) * 1981-02-03 1982-08-13 Toray Ind Inc Selective permeable membrane

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5009824A (en) * 1981-12-17 1991-04-23 Hoechst Aktiengesellschaft Process for preparing an asymmetrical macroporous membrane polymer
US5176724A (en) * 1987-11-10 1993-01-05 Matsushita Electric Industrial Co., Ltd. Permselective composite membrane having improved gas permeability and selectivity
US4859215A (en) * 1988-05-02 1989-08-22 Air Products And Chemicals, Inc. Polymeric membrane for gas separation
US5011518A (en) * 1989-03-09 1991-04-30 Matsushita Electric Industrial Co., Ltd. Permselective membrane and process for producing the same
US4968470A (en) * 1989-11-15 1990-11-06 Air Products And Chemicals, Inc. Asymmetric permselective polyacetylene membranes and process for the formation thereof
US5085676A (en) * 1990-12-04 1992-02-04 E. I. Du Pont De Nemours And Company Novel multicomponent fluid separation membranes
US5318706A (en) * 1991-03-06 1994-06-07 Hashimoto Chemical Co., Ltd. Method of supplying dilute hydrofluoric acid and apparatus for use in this method for supplying the acid
US5762798A (en) * 1991-04-12 1998-06-09 Minntech Corporation Hollow fiber membranes and method of manufacture
US5156656A (en) * 1991-09-13 1992-10-20 The Dow Chemical Company Semi-permeable membranes derived from reactive oligomers
DE4213217A1 (en) * 1992-04-22 1993-10-28 Geesthacht Gkss Forschung Membrane based on graft copolymers
DE4213217C2 (en) * 1992-04-22 1999-11-25 Geesthacht Gkss Forschung Membrane based on graft copolymers, graft copolymene and process for their production
USRE36914E (en) * 1992-10-07 2000-10-17 Minntech Corp Dialysate filter including an asymmetric microporous, hollow fiber membrane incorporating a polyimide
US5281255A (en) * 1992-11-04 1994-01-25 Membrane Technology And Research, Inc Gas-separation process
US5501722A (en) * 1992-11-04 1996-03-26 Membrane Technology And Research, Inc. Natural gas treatment process using PTMSP membrane
US5599380A (en) * 1994-05-20 1997-02-04 L'air Liquide, S.A. Polymeric membrane
US5858065A (en) * 1995-07-17 1999-01-12 American Air Liquide Process and system for separation and recovery of perfluorocompound gases
US5785741A (en) * 1995-07-17 1998-07-28 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges, Claude Process and system for separation and recovery of perfluorocompound gases
US6605133B1 (en) 1995-07-17 2003-08-12 L'air Liquide - Societe Anonyme A' Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude Process and system for separation and recovery of perfluorocompound gases
US6224677B1 (en) 1995-07-17 2001-05-01 Teisan Kabushiki Kaisha Gas recovery unit utilizing dual use of gas
US5919285A (en) * 1995-07-17 1999-07-06 American Air Liquide, Inc. Process and system for separation and recovery of perfluorocompound gases
US6444011B2 (en) 1995-07-17 2002-09-03 American Air Liqide, Inc. Process and system for separation and recovery of perfluorocompound gases
US6312502B1 (en) * 1995-07-17 2001-11-06 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process and system for separation and recovery of perfluorocompound gases
US6254666B1 (en) 1995-07-17 2001-07-03 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process and system for separation and recovery of perfluorocompound gases
US6214089B1 (en) * 1995-07-17 2001-04-10 American Air Liquide, Inc. Process and system for separation and recovery of perfluorocompound gases
US5759237A (en) * 1996-06-14 1998-06-02 L'air Liquide Societe Anonyme Pour L'etude Et, L'exploitation Des Procedes Georges Claude Process and system for selective abatement of reactive gases and recovery of perfluorocompound gases
US5707423A (en) * 1996-06-14 1998-01-13 Membrane Technology And Research, Inc. Substituted polyacetylene separation membrane
US5814127A (en) * 1996-12-23 1998-09-29 American Air Liquide Inc. Process for recovering CF4 and C2 F6 from a gas
US5968334A (en) * 1996-12-23 1999-10-19 American Air Liquide Inc. Process for recovering CF4 and C2 F6 from vent gases of an aluminum production cell
US6096114A (en) * 1997-05-15 2000-08-01 American Air Liquide, Inc. Process for recovering SF6 from a gas
US5855647A (en) * 1997-05-15 1999-01-05 American Air Liquide, Inc. Process for recovering SF6 from a gas
US6187077B1 (en) 1998-04-17 2001-02-13 American Air Liquide Inc. Separation of CF4 and C2F6 from a perfluorocompound mixture
US20040194513A1 (en) * 2003-04-04 2004-10-07 Giacobbe Frederick W Fiber coolant system including improved gas seals

Also Published As

Publication number Publication date
JPH0147210B2 (en) 1989-10-12
WO1983001905A1 (en) 1983-06-09
JPS5895541A (en) 1983-06-07

Similar Documents

Publication Publication Date Title
US4714481A (en) Gas separation membrane
Fadeev et al. Extraction of butanol from aqueous solutions by pervaporation through poly (1-trimethylsilyl-1-propyne)
US4657564A (en) Fluorinated polymeric membranes for gas separation processes
US7179325B2 (en) Hydrogen-selective silica-based membrane
US4759776A (en) Polytrialkylgermylpropyne polymers and membranes
JPS62723B2 (en)
CN112851690B (en) Low-molecular-weight self-microporous polymer, preparation method thereof, ultrathin organic solvent nanofiltration membrane and preparation method thereof
Matson et al. Synthesis, Structure and Properties of Poly (1-Trimethylsilyl-1-Propyne) Obtained with NbBr 5-and TaBr 5-Based Catalytic Systems
US4746334A (en) Poly(disubstituted acetylene)/polyorganosiloxane graftcopolymer and membrane for gas separation
Lin et al. Excellent permselective membranes of diphenylacetylene copolymers with hydroxy groups
Li et al. Gas permeability of high-temperature-resistant silicone polymer-vycor glass membrane
JPS60212414A (en) Acetylenic polymer and separating membrane consisting thereof
JP2910898B2 (en) Method for separating alkanol having 1 to 3 carbon atoms from another organic solution
JPH0536091B2 (en)
JPS59169507A (en) Gas separation membrane
JPH0692483B2 (en) Polysulfone-based graft copolymer
KR101756320B1 (en) Polysilsesquioxane Polymer, Gas Separation Membrane And Method For Preparation Thereof
US5171794A (en) Modified poly(2,6-dimethyl-p-oxyphenylene), a process for its preparation and its use in gas mixture separation membranes
EP0245516A1 (en) Polymer membrane for separating liquid mixture
JP4883683B2 (en) Organopolysiloxane for gas separation membrane
US4755561A (en) Poly(disubstituted acetylene)/polyorganosiloxane graft copolymer and membrane for gas separation
JPH0140644B2 (en)
JPH0221856B2 (en)
Sakaguchi et al. Synthesis and gas permeability of methylol-group-containing Poly (diphenylacetylene) s with high CO2 permeability and permselectivity
JPH0459325B2 (en)

Legal Events

Date Code Title Description
AS Assignment

Owner name: MITSUBISHI CHEMICAL INDUSTRIES LIMITED, 5-2, MARUN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:MATSUURA, JUNICHI;OKADA, MUNEHISA;REEL/FRAME:004763/0136

Effective date: 19830704

Owner name: MITSUBISHI CHEMICAL INDUSTRIES LIMITED,JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MATSUURA, JUNICHI;OKADA, MUNEHISA;REEL/FRAME:004763/0136

Effective date: 19830704

AS Assignment

Owner name: MITSUBISHI KASEI CORPORATION

Free format text: CHANGE OF NAME;ASSIGNOR:MITSUBISHI CHEMICAL INDUSTRIES LIMITED;REEL/FRAME:005004/0736

Effective date: 19880601

Owner name: MITSUBISHI KASEI CORPORATION, JAPAN

Free format text: CHANGE OF NAME;ASSIGNOR:MITSUBISHI CHEMICAL INDUSTRIES LIMITED;REEL/FRAME:005004/0736

Effective date: 19880601

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 4

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
FP Lapsed due to failure to pay maintenance fee

Effective date: 19951227

STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362